J. Pure App. Chem. Res.

, 2015, 4 (1), 17-24

12 March 2015

Influenceof Dye Adsorbtion Time on TiO2 Dye-Sensitized Solar

Cells with Krokot Extract (Portulaca oleracea L.) as
A Natural Sensitizer
Siti Khuzaifah,1 Didik Krisdiyanto,1* Khamidinal,1 and Endaruji Sedyadi1
1

Department of Chemistry, Faculty of Science and Technology, UIN Sunan Kalijaga,

Jl. Marsda Adisucipto No. 1 Yogyakarta 55281, Indonesia
*

Corresponding email: didik_kris@yahoo.com

Received 29 December 2014; Accepted 11 March 2015

ABSTRACT
Dye sensitized solar cells (DSSC) photoelectrodes were fabricated using titanium oxide
(TiO2) and sensitized with the krokot extract dye. This study investigated the effect of dye
adsorbtion time to an efficiency of the solar cells. The fabrication cells immersed with
krokot extract dye for 1, 8, and 26 hours. The photochemical performance of the DSSC
showed that the open circuit voltage (Voc) were 0.33, 0.036 and 0.27 V with short
photocurrent density (Isc) 8.00 x 10-5, 6.80 x 10-7 and 3.10 x 10-4. The photo-to-electric
conversion efficiency of the DSSC reached 4.63 x 10 -3 % for 26 hours adsorbtion time.
Keywords: dye sensitized solar cells (DSSC), krokot extract dye, titanium oxide

INTRODUCTION
The solar cell is one way to harness solar energy in which the device is able to convert
the sunlight energy into electrical energy. In principle, the solar cell work is similar to the
photosynthesis work in plants. Light energy is used to produce free electrons. Solar cell uses
free electron to generate electrical energy while the plant uses the free electron to produce
chemical energy [1]. The development of solar cells based on dye sensitized began in 1991
when for the first time Grtzel and O'Regan designed the basic forms of solar cell based on
film of titania semiconductor that is known as dye-sensitized solar cell (DSSC) in which
these systems can convert solar energy into electrical energy [2]. This mechanism shows the
optical absorption and charge separation processes through the association of a sensitizer as a
light absorber with a nano crystal semiconductor that has a wide band gap [3].
A DSSC consists of a pair of coated glass TCO substrate (Transparent Conducting
Oxide) as the electrode and the counter electrode, the redox electrolyte that contains iodide
and tri-iodide ion (I - /
carbon layer as the catalyst, porous TiO2 nano crystal as photo
anode, and a dye photosensitizer [2]. All components are arranged in front of the sandwich
structure where the top layer is the working electrode as the initial layer in receiving photons
and the lower layer is the counter electrode and the middle is electrolyte to regenerate
electron. Dye criteria that can be used as a dye sensitizer is adsorption intensity at visible
wavelengths, strong adsorption on the surface of the semiconductor, has the ability to inject
electrons to the band conduction of the semiconductor, and has a group =O or -H to bind to
the surface of TiO2 which can increase the reaction rate of the electron transfer [4]. Krokot
extract contained some compounds such as oxalic acid, caffein, maleic acid, alkaloid,
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

17

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

coumarin, flavonoid, cardiac glycoside, anthraquinone, glycoside, alanine, catechol, saponin,

and tannin [5]. Flavonoid composed of kaempferol, apigenin, myricetin, quercetin, and
luteolin [6,7].
Another fabrication factor is the dye adsorption time, which determines the quantity
and the nature of the adsorbed dye molecules. The dye adsorption time should be sufficiently
long, so that the interfacial surface of the oxide film is completely covered with a monolayer
of dye molecules. In fabricating TiO2-based photoanodes, the length of the dye adsorption
time is determined. This is because TiO2 is insensitive to prolonged sensitization times
because of its higher chemical stability [8-10]. Ideally the oxide surface should be covered
with a monolayer of dye molecules to achieve efficient electron injection. When dye
molecules undergo aggregation, electron injection becomes less efficient, and overall
conversion efficiency declines. For TiO-based cells, it is essential to optimize the dye
adsorption time to minimize the formation of dye aggregates and the damage to TiO2
surfaces. Because the dye molecules must penetrate the mesoporous oxide film before they
attach to the interfacial surface, the optimal dye adsorption time likely depends on the
thickness of the TiO film. Thus, this study investigates the dye adsorption time was
important. Although these factors have been reported the influences of dye concentration
adsorption time on DSSC performance [11,12]. Therefore, this study utilize the potential of
the natural dye that derived from extracts of krokot which are expected to fulfill the
requirement as a natural sensitizer. Optical and electrical test are done in order to determine
the compliance of the requirement and can be used in DSSC system. To further understand
the effect of dye adsorption time was used to investigate the electron transport characteristics
of the fabricated cells. This study shows the correlation between efficiency and dye loading
as a function of the dye adsorption time.

Figure 1. DSSC with krokot extract dye sceme

EXPERIMENT
Chemicals and instrumentation
Chemicals used for research are krokot (Portulaca oleracea L.), Indium Transparent
Oxide (ITO), TiO2 (degusa), KI, I2, polyethylene glycol, ethanol 96%, Polyvinyl alcohol
(PVA), aquadest, graphite pencil 8B and detergent.
Instrumentation applied for research are ultrasonic cleaner, hotplate, glassware,
aluminium foil, paper clips, scothlite, UV-Vis spectrophotometers single beam, UV-Vis
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

18

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

specular reflectance, Fourier transform infrared spectroscopy (FT-IR) Shimadzu and I-V
meter Keithley 2400.
Preparation of krokot (Portulaca oleracea L) extract
Ten grams of krokot powder are macerated with 120 mL of 96% ethanol for 24 hours.
Then, it is filtered by using vacuum filtration and before it is used for further processing, it
should be analyzed first using UV-Vis spectrophotometer in the wavelength range 400-700
nm.
Preparation of working electrode
TiO2 powder was weighed as much as 1.5 g and then inserted into an erlenmeyer and
added with 3.0 mL of aquadest. Then, it is stirred with a magnetite stirring spoon and
sonicated with 20 kHz frequency for 2 hours. The next solution was then added with
polyvinyl alcohol solution which previously has been made from 0.5 g PVA added with 6.0
mL of aquadest by heating at temperature of 150oC until all of PVA were dissolved. The
mixing is followed by stirring for 10 minutes until homogeneous. Then, it is performed TiO2
paste deposition on surfaces glass of ITO with Doctor Blanding technique. But before it, ITO
should be washed with detergent and followed by aquadest using ultrasonic cleaner for 10
minutes and rinsed with ethanol. Before TiO2 paste is dropped on ITO glass, the conductive
part should be found and then each of it was given a double tape restraint and it was made a
rectangular pattern by leaving a 1.8 by 1.3 cm room. Furthermore, in above of that field, the
TiO2 paste was distributed evenly with a glass rod and then dried in the air and the scotchlite
was opened, then it is heated at 80 C for 1 hour.
Preparation TiO2/dye electrode
TiO2 film is inserted into the krokot extract, the container is covered with aluminum foil
and then it is saved for 1, 8, 18 and 26 hours. The film which has been soaked then removed
and rinsed with ethanol to clean the edge of the layer. Then it was dried at room temperature
and analyzed by UV-Vis reflectance spectrometer and FT-IR.
Preparation of the counter electrode
The graphite pasted into the surface of ITO on the conductive layer with the shading
manner to average carbon layer. Then, it is heated at temperature of 300 oC for 1 hour.
Preparation of electrolytes
Potassium iodide (KI) is weighed as much as 0.815 g and then dissolved in 10 mL of
polyethylene glycol (PEG) 400 and stirred until dissolved. Then it was added with 0.128 g of
I2 and stirred again until completely mixed. The finished electrolyte solution was stored in the
dark bottle and also well sealed.
Fabrication of Dye-Sensitized Solar Cell (DSSC)
DSSC fabrication which was and wich construction consist of glass-ITO working
electrode (TiO2 layer) that has been coated with dye-screen projector-counter electrode
(carbon layer)ITO glass. The use of screen to prevent the short on DSSC system. At the
ends of the glass that does not stick together is spilled with the electrolyte solution and
allowed to combine between the two layers after it is clamped with paper clip on two
opposite sides are not coated.
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

19

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

Characterization of currents and voltage of DSSC

DSSC prototype was tested by measuring the I-V characteristic curve using a digital
multimeter Keithley2400, in the light of a xenon lamp at an intensity of 1000 W/m2. The
result of the I-V characteristic curves test were then analyzed Voc, Isc, fill factor, and the
efficiency of solar cells [6] by the equation:
FF=
(1)
=

(
(

(
)

(2)

RESULT AND DISCUSSION

Characterization the optical properties of krokot extract
Figure 2 demostrates the UV-VIS absorption spectra of extract krokot dye. It was
found that the absorption peak is about 420.5, 536.5, 608 and 665.5 nm. The absorption
maximum peaks are 420.5 and 665.5 nm suggest to chlorophyll adsorption. So that
chlorophyll can be used as a dye in DSSC because it has characteristic to absorb the visible
light that produced by sunlight.

Figure 2. (right)
Absorption
spectra of extract
krokot dye
(rught)

Characterization of electronic properties TiO2-dye

Figure 3 shows the absorption spectrum of TiO2 film sensitized by different dye
adsorption time.It aims to find out that the longer the adsorption time so there are more dye
that are absorbed on the surface of TiO2 so that there are more electrons will be generated.
From the figure it can be seen that the TiO2 has a high absorption in the ultraviolet light
region and the low absorption in the region of visible light. The addition of the dye serves as
a sensitizer to increase the absorption area of the semiconductor. It is seen that the addition of
the dye will enhance the ability of TiO2 electrode layer to absorb the visible region.
In the TiO2 sample testing, the maximum absorbance at a wavelength of 326 nm and
then increased to 332 nm when is done immersion in the dye for 1 hour. There was a
decreasing became 331 nm after 8 hours immersion and 315 nm after 18 hours immersion
and increased back to 337 nm after 26 hours immersion. The increasing of wavelength
irregularities are due to the number of molecules in the dye that can cause steric effects then
cause the interaction of the dye with a film of TiO2 not optimal.
Absorbance is used to calculate the band gap energy (Eg) in the film of TiO2 and TiO2dye film with different adsorption time by Tauc plot method. Figure 4 shows the form of the
TiO2 band gap is 3.3 eV. This value reach the major requirements of semiconductor material
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

20

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

that will be used as a DSSC where its band gap energy should more than 3.0 eV so that be
able to absorb the energy of the photon in the most of the spectrum of sunlight.

Figure 3 (Right) The graph of

absorbance to wavelength (A) thin
layer TiO2, (B) thin layer TiO2-dye 1
hour, (C) thin layer TiO2-dye 8 hour,
(D) thin layer TiO2-dye 18 hour, and
(E) thin layer TiO2-dye 26 hour

Figure 4. Energy gap (A)

thin layer TiO2, (B) thin
layer TiO2-dye 1 hour, (C)
thin layer TiO2-dye 8 hour,
(D) thin layer TiO2-dye 18
hour, and (E) thin layer
TiO2-dye 26 hour
Figure 4 shows the band gap energy (Eg) of TiO2 with different dye adsorption time.
TiO2 with an hour adsorption time was 3.45 eV. Meanwhile band gap energy (Eg) for 8, 18
and 26 hours adsorption time indicates a consecutive decreasing to 3.30, 3.25, and 3.10 eV.
This is as expected that the longer of the TiO2 film immersion in dye capable to decrease Eg
on TiO2 so that allowing the electrons injection of dye sensitized into the conduction band of
nanoparticles TiO2 becomes easier because it takes a lower photon for excitation mechanism
or in other words the deposited TiO2 has been more active in the area of low energy or visible
light region.
Characterization with FT-IR spectrophotometer
Infrared absorption spectrum of a material has a distinctive pattern to identify the
material and also shows the existence of the major functional groups in the identified
structure. The FTIR spectra of TiO2-dye system shows the appearance of a significant new
peak or functional groups shift if it is compared with the spectra of dye and spectra of TiO2
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

21

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

film. Krokot extract contains carboxyl and carbonyl groups of chlorophyll that possible to
form a chemical bond with TiO2.
The results of FTIR analysis for TiO2 film and TiO2-dye film of krokot extract is
shown in the Figure 5. This shows the existence of the carbonyl absorption at wave number
1627.92 cm-1 and absorption at 3425.58 cm-1 region is the absorption area for hydroxyl
groups. Carbonyl and hydroxyl groups that is owned by krokot extract can bind to the group
of Ti(IV) on TiO2.
The FTIR spectra resulted (Figure 5) indicates no significant difference from treatment
with variation of immersion. It is only seen the carbonyl absorption shift of in TiO2 film is at
a wavelength of 1635.64 cm-1 shifted to a wave number 1627.92 cm-1. This shift occurs when
a film of TiO2 is coated with krokot extract and relatively constant for the time variation of 1,
8, and 26 hours and does not change for 18 hours. This shows that krokot extract does not
bind yet optimally with a TiO2 film or the possibly interaction occur as physical interaction.
Figure 5 (right). The
infrared spectra of (A)
krokot extract, (B) thin
layer of TiO2, (C) thin layer
of TiO2-dye 1 hour, (D) thin
layer TiO2-dye 8 hour, (E)
thin layer TiO2-dye 18 hour,
and (F) thin layer TiO2-dye
26 hour

Current and voltage measurement systems solar cells

The manufactured of DSSC consists of the working-electrode, counter electrode and
the electrolyte. The arranging is made from sandwich system which is then tested using the IV meter Keithley 2400 for current characteristics and the voltage at the DSSC. The presence
of irradiation by the light source to the sample surface will increase the electron-hole pairs.
Electron-hole pairs will be separated by an electric field which is then contributes to the
increased flow. When the voltage at the maximum position, then, there is no current flowing
and so it is called as voltage open circuit (Voc). Instead voltage is zero when the flow/current
is occurred in the short-circuit (Isc).
In Table 1 was summarized the efficiency obtained by determining the amount of
voltage and the maximum current shown in the Figure 5. From that figure, it can be seen that
the current legible shows the dye on TiO2 layers undergo the electron transfer from the
excited state of the dye to the conduction band of TiO2. The highest efficiency found in a
layer of TiO2-dye with an absorption time of 26 hours with an efficiency of 4.63 x 10-3%.
The current value, which is very small, indicates the presence of the cell electrolyte
leakage due to construction of DSSC which are not meeting between the working electrode
and the counter electrode. Possibly because it is only clamped with paper clipper and the
carbon which serves as a catalyst redoxs reaction is not functioning optimally. As the result
the redox reaction in the electrolyte is not running perfectly. It causes the exchange of
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

22

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

electrons from the redox reaction cannot counter balance with the generation of electrons
from the dye sensitization so that the overall value of the current-flowing becomes small and
influence the efficiency of solar cells tested.
Table 1. The parameters of solar cells
Characterization
I-V

Thin layer
TiO2

Vmax (V)
Imax (A)
Pmax (W)
Isc (A)
Voc (V)
Fill Factor
efficiency (%)

0.027
1.00 x 10-5
2.70 x 10-7
1.60 x 10-5
0.08
0.2109
6.52 x10-5

Thin layer
TiO2-dye
1 hour
0.175
4.50 x 10-6
7.87 x 10-6
8.00 x 10-5
0.33
0.2982
1.90 x10-3

Thin layer
TiO2-dye
8 hour
0.02
6.80 x 10-7
1.36 x 10-8
6.80 x10-7
0.036
0.5555
3.28 x 10-6

Thin layer
TiO2-dye
26 hour
0.12
1.60 x 10-4
1.92 x 10-5
3.10 x 10-4
0.27
0.2293
4.63 x 10-3

In this study, the small DSSC efficiency was afforded possibly because the
performance of natural dye extracted form krokot plant still contains a lot of pigment with
long alkyl groups. This group that normally with consist of long alkyl group provided the
steric hindrance effect to the surface band and this also affected on the oxidation of TiO2
molecules to bind with TiO2. Due to this limitation then the transfer of electrons from the
conduction band to the dye molecule is reduced.
CONCLUSION
The result shows that the absorbance spectrum of the krokot extract dye is stretched in
the range of visible light to the maximum absorbance peak at a wavelength of 420.5 nm and
665.5 nm. It summarized the presence of chlorophyll. There is a decrease of the energy gap
of TiO2 film which is sensitized with krokot extract with the variation of dye adsorbtion time
of 3.3 eV for TiO2 film to 3.10 eV after 26 hours adsorption time. The results of TiO2 film
and after sensitized by krokot extract with different adsorption time show no significant shift
in functional group and also there is an increasing of efficiency of 6.52x10-5% for TiO2 film,
1.90x10-3% for an hour adsorption time to 4.63 x 10-3% for 26 hours.
ACKNOWLEDGMENT
Department of Chemistry, Faculty of Science and Technology UIN Sunan Kalijaga
Yogyakarta for academic supported. This paper was presented at Joint Indonesia-UK
Conference on Organic and Natural Product Chemistry 10-11 December 2014.
REFERENCES
[1]. Yuwono, A. H., Dhaneswara, D., Ferdiansyah, A., Rahman, A., Jurnal Material dan
Energi Indonesia, 2011, 1, 127-140.
[2]. O'Regan, B., Gratzel, M., Nature, 1991, 353, 737-740
[3]. Gratzel, M., J. Photoch. Photobio. A, 2003, 4, 145,153.
[4]. Ludin, N. A., Narosikin, A. A. M., Mahmoud, A. A., Muhammad, A. A., Kadhum A.
A. H., Sopian, K., Nor Karim, S. A., Renew. Sust. Energ. Rev., 2014, 31, 386-396.
The journal homepage www.jpacr.ub.ac.id
ISSN : 2302 - 4690

23

J. Pure App. Chem. Res., 2015, 4 (1), 17-24

12 March 2015

[5].
[6].
[7].
[8].
[9].

Mohammad, T. B., Mohammad, H. B., Farhad, M., Iran. J. Pharm., 2004, 3, 84-90.
Xu, X., Yu, L., Chen, G., Pharm. Biomed. Anal., 2005, 41, 493-499.
Zhou, H., Wu, L., Gao, Y., Ma, T., J. Photoch. Photobio. A, 2011, 219, 188-194.
Chou, T. P., Zhang, Q. F., Cao, G. Z., J. Phys. Chem. C, 2007, 111, 18804-18811
Lee, K. M., Suryanarayanan, V., Huang, J. H., Thomas, K. R., Lin, J. T., Ho, K. C.,
Electrochim. Acta, 2009, 54, 41234130.
[10]. Kim, J. K., Seo, H., Son, M. K., Shin, I., Hong, J., Kim, H. J., Curr Appl Phys, 2010,
10, 418421.
[11]. Horiuchi, H., Katoh, R., Hara, K., Yanagida, M., Murata, S., Arakawa, H., Tachiya, M.,
J. Phys. Chem. B, 2003, 107, 25702574.
[12]. Keis, K., Lindgren, J., Lindquist, S.E., Hagfeldt, A., Langmuir, 2000, 16, 46884694.

The journal homepage www.jpacr.ub.ac.id

ISSN : 2302 - 4690

24